Quaternary ammonium xanthates



2,812,332 Patented Nov. 5, 195? QUATERNARY AMMONIUM XANTHATES Charles J.Pennino, Hudson, Ohio, assignor to The B. F. Goodrich Company, New York,N. Y., a corporation of New York 1 No Drawing. Application April 1,1955,

Serial No. 498,771

13 Claims. (Cl. 260-294.8)

and useful quaternary ammonium alkyl and alkenylxanthates.v

Another object is the provision of quaternary am- '2 butyl, isobutyl,and allyl xanthates; benzyl trimethyl ammonium methyl, ethyl, propyl,isopropyl, butyl, isobutyl and a-llyl Xanthates; cetyl dimethyl benzylammonium methyl, ethyl, propyl, isopropyl, butyl, isobutyl 5 .and allylxa'nthates; methyl pyridinium methyl, ethyl,

monium lower alkyl and alkenyl xantha tes which have high degrees ofbiological activity.

Still another object is the provision of quaternary ammonuim compoundsin which the anion is a lower alkyl or alkenyl xanthateradical. V I

Yet another object is the provision of a method for preparing quaternaryammonium lower alkyl and alkenyl xanthates by reacting a quaternaryammonium'halide with an alkali metal lower alkyl or alkenyl Xanthate.

The quaternary ammonium 'xanthates of this invention have uniquebioligical properties which make them useful as bacteriostatic orbactericidal agents, as fungicides, herbicides, algicides, insecticidesand as preservatives for cellulosic materials.

The compounds have the generic structure where R and R1 each representsa methyl group and one valence of the hydrocarbon residue of a pyridinenucleus, R2 represents a methyl, a benzyl hydrocarbon group and onevalence of the hydrocarbon residue of a pyridine nucleus, and R3represents an aliphatic hydrocarbon group having from 1 to 20 carbonatoms, an aryl group, and an alkaryl group, and Y represents a loweralkyl or lower alkylene group having from 1 to 4 carbon atoms.

Typicalcompounds of the type described are tetramethyl ammonium methyl,ethyl, propyl, isopropyl, butyl, isobutyl and allyl xanthates; butyltrimethyl ammonium methyl, ethyl, propyl, isopropyl, butyl, isobutyl andallyl xanthates, octyl trimethyl ammonium, methyl, ethyl, propyl,isopropyl, butyl, isobutyl and allyl xanthates; decyl trimethyl ammoniummethyl, ethyl, propyl, isopropyl, butyl, isobutyl and allyl xanthates;dodecyl trimethyl ammonium methyl, ethyl, propyl, isopropyl, butyl,isobutyl and allyl Xanthates; tetradecyl trimethyl ammonium methyl,ethyl, propyl, isopropyl, butyl, isobutyl and allyl xanth-ates;octadecyl trimethyl ammonium methyl, ethyl, propyl, isopropyl, butyl,isobutyl and allyl Xanthates; octadecenyl trimethyl am-- monium methyl,ethyl, propyl, isopropyl, butyl, isobutyl and allyl xanthates;p-diisobutylphenoxyethoxyethyl dimethyl benzyl ammonium methyl, ethyl,propyl, isopropyl, butyl, isobutyl and allyl xanthates; phenyltrimethylammonium methyl, ethyl, propyl, isopropyl,

propyl, isopropyl, butyl, isobutyl and. allyl 'Xanthates; butylpyridinium methyl, ethyl, propyl, isopropyl, butyl, isobutyl and allylxanthates; octyl pyridinium methyl, ethyl, propyl, isopropyl, butyl,isobutyl and allyl xanthates; decyl pyridinium methyl, ethyl, propyl,isopropyl, butyl, isobutyl, and allyl xanthates; dodecyl pyridiniummethyl, ethyl, propyl, isopropyl, butyl, isobutyl and allyl xanthates;octadecyl pyridinium methyl, ethyl, propyl, isopropyl,buty1, isobutyland allyl xanthates;

voctadecenyl pyridinium methyl, ethyl, propyl, isopropyl,

butyl, isobutyl, and allyl xanthates, and benzyl pyridinium methyl,ethyl, propyl, isopropyl, butyl, isobutyl, and allyl xanthates. Thepreferred compounds are those which have an aryl group or an alkyl grouphaving at least 12 carbon atoms or those prepared from pyridines inwhich the hydrocarbon portion of the pyridine residue is attacheddirectly to the quaternary nitrogen atom. These compounds are preparedby dissolvinga quaternary ammonium halide in water, adding an alkalimetal salt of a lower alkyl or lower alkenyl Xanthate. A chemicalreaction occurs, whereby the halide of the quaternary ammonium compoundis replaced by a xanthate radical, in accordance with' the followingequation.

CH CH3 n-dodecyl trimethyl ammonium ethyl xanthate If a quaternaryammonium xanthate free'of a metal halide is desired it can be preparedby the use of a diluent in which the quaternary ammonium halide andalkali metal xanthate are soluble, but in which the alkali metal halideis insoluble. One specific procedure is to prepare a solution of aquaternary ammonium halide in an alcohol, such as .isopropanol, add therequisite amount of the appropriate alkali metal Xanthate, such assodium Xanthate, cool the mixture to permit crystallization of thesodium halide, and filter the solution of quaternary ammonium xanthateto remove the sodium halide. Numerous other inert diluents havingtheabove-described characteristics can be employed in place of'isopropanol.

It is to be understood that other quaternary ammonium halides will reactwith other alkyl or alkenyl xanthates in the same manner as thatdescribed above.

The quaternary ammonium Xanthates are soluble in benzene and otherliquid aromatic hydrocarbon solvents and can therefore 'be easilyseparated from the reaction mixture. If desired, however, the quaternaryammonium Xanthates can be left in the reaction mixture, and the or otherliquid, inert, aromatic organic solvents, or as dusts admixed with talc,kieselghur, clay, chalk or other solid, inert fluent carriers. Anadhesive ingredient such as a rubber or synthetic resin latex, fish orvegetable oil, heavy mineral oil or other adhesive material can be addedto the liquid compositions containing the quaternary ammonium xanthatesto permitas long a contact time as possible in order that the completeaflFect of the biological activity of the compounds can be exerted onthe treated materials.

The quaternary ammonium xanthates will vary somewhat in their biologicalactivity depending in part on the structure of the cationic portion ofthe molecule and in part on the anionic portion. In general a long chainalkyl or alkenyl hydrocarbon group with about 12 carbon atoms or more asthe cation broadens the spectrum of biological activity. The compoundswith a phenyl or benzyl group in the cation are of intermediate activityand those which have only the lower alkyl groups, such as thetetramethyl ammonium xanthates are less active. The difference inactivity due to the length of the carbon chain in the anion are not aspronounced as those of the cation. However, the presence of the ExampleI A solution of n-dodecyl trimethyl ammonium chloridein water containing33% by weight of the chemical was prepared, and 79.5 parts were warmedto 50-60 C. A solution containing 18 partsof sodium isopropyl xanthatein 100 parts of water was added with stirring to the warmed quaternaryammonium halide solution. Two liquid phases resulted, the top being aviscous, oily organic layer. The aqueous phase was extracted withbenzene and then combined with the organic liquid layer, and thesolution was then dried with anhydrous sodium sulfate and the solventdistilled under vacuum to yield 36.1 parts of residue, which yield isquantitative. An

analysis of the compound showed the following results.

Percent Percent Percent H N Calculated for omnmosl 11. 31 1 3.32

. 11. a. Fmmd In a biological assay wherein this new compound wascompared directly with n-dodecyltrimethyl ammonium chloride at the sameconcentration by weight it was found that at 100 p. p. In. bothprevented the germination of spores of A. olcracea. The chloride left aclear zone 4.5 cm. in diameter and the xanthate a 6-8 cm. zone whentested against S. fructicola by the filter paper disc method. Cottonduck treated with the chloride in a soil burial test retained 24% of itsoriginal strength, Whereas the duck treated with the xanthate retained77% of its original strength. In addition the xanthate is a betterherbicide than the chloride.

Example 11 used as one reactant in water with a slight excess of isofromsoya oil.

propyl xanthate as the second reactant. The reaction conditions weresubstantially the same as those described in Example I. The quaternaryammonium xanthate that formed, was a viscous liquid with a density lessthan that of the aqueous phase of the reacted mixture. The R3 group ofthe generic structure in the quaternary ammonium xanthate containedaliphatic carbon chains with a length of from 8 to 18 carbon atoms, themajor proportion being C12.

The biological activity of this quaternary ammonium xanthate wascompared directly with the quaternary ammonium chloride which was usedas one reactant in the preparation of the xanthate. The sterile zone inthe filter paper disc test against S. fructicola for the xanthate wasmore than 7 cm. in diameter, as compared with a zone of 4.5 cm. for thechloride. In the cotton duck burial test, the cloth treated with thexanthate .did not lose any of its strength, but the cloth treated withthe chloride had only 60% of is strength at the end of the same periodof time. Kraft paper was also protected from deterioration in soil to avastly greater degree by the xanthate when compared with the chloride,and the xanthate was also a better herbicide than the chloride.

Example III A quaternary ammonium xanthate was prepared from aquaternary ammonium chloride, which had three methyl groups and thehydrocarbon residue of amines made The soya-amine moiety had a carbonlength of from 8 to 18 carbon atoms.

A slight excess of sodium isopropyl xanthate was used. The procedure wassimilar to that of Example I. This end product was an oil which waspurified by solution in benzene and distillation of the solvent.

The quaternary ammonium xanthate was outstanding in its ability toprotect cotton duck and paper from deterioration by soil microorganisms,whereas the quaternary ammonium chloride was only fair in this respect,and the herbicidal activity of the xanthate was superior to that of thechloride.

Example IV A series of other alkali metal xanthates, namely, sodiumethyl, allyl and isobutyl xanthates, was used in preparing derivativesof n-dodecyltrimethyl ammonium chloride. The anion in the end productcorresponded to that of the alkali metal xanthate used in the reaction,and the cation in each instance had the following structure The methodused was the same as that previously described. Each of these quaternaryammonium xanthates is a viscous liquid at room temperature, and each isa good fungicide, bactericide and herbicide. The mathates are all goodprotective agents for cotton duck, and much superior to the chloride.n-Dodecyl trimethyl ammonium allyl xanthate is a very powerful broadspectrum bactericide.

Example V Phenyl trimethyl ammonium isopropyl xanthate was prepared byreacting a slight excess of potassium isopropyl xanthate wth phenyltrimethyl ammonium chloride in aqueous media at a temperature ofapproximately 50 to 60 C. This quaternary ammonium xanthate was a verygood protective agent against the decomposition of kraft paper andcotton duck in soil burial tests. The herbicidal activity, however, wasnot as high as the dodecyl derivatives described above. The compound iscrystalline with a melting point of 119-121? C. and is slightly solublein water and quite soluble in benzene, which property makes it possibleto purify and recrystallize the compound.

Example VI A series of lower alkyl xanthate derivatives were prepared byreacting sodium alkyl xanthates with lauryI pyridinium chloride(technical) in water at a slightly elevated temperature, usually nothigher than about 60 CJThe xanthates that were reacted included sodiumethyl xanthate, sodium n-propyl xanthate, sodium isopropyl xanthate,sodium allyl xanthate, sodium n-butyl xanthate and sodium isobutylxanthate. In all instances the xanthate salt of the quaternary amine wasa viscous liquid which formed a supernatant layer in the aqueousreaction system. Separation was made by dissolving the quaternaryammonium xanthate in benzene and washing with saturated salt solutionwhile maintaining the'temperature at about 50 C. The benzene solutionwas dried with anhydrous sodium sulfate and the solvent was distilledoil under vacuum. The residue of the lauryl pyridinium isopropylxanthate when weighed amounted to a quantitative yield. This was driedunder vacuum and analyzed for carbon, hydrogen and sulfur. The resultsof this analysis are as follows:

Calculated for C21H37NOS: (C21 av. chain The yields for the otherxanthatesare also substantially quantitative. When tested forbactericidal activity by the filter paper disc method against S. aureusthe ethyl xanthate derivative yielded a clear zone of 5.6 cm.; propylxanthate 7 cm.; the isopropyl xanthate 5.3 cm.; the allyl xanthate 5.6cm.; the butyl xanthate 4.8 cm.; and the isobutyl xanthate 5.8 cm. Theoriginal quaternary ammonium chloride used in preparing the xanthatederivatives had a clear zone of 3.8 cm. The ethyl xanthate, isopropylxanthate, butyl xanthate and isobutyl xanthate quaternary ammonium saltswere excellent protective agents against the deterioration of cottonduck by soil microorganism and each piece of duck treated with xanthatesalts retained a minimum of 83% of its strength whereas the quaternaryammonium chloride treated duck retained only 60% of its strength. Theethyl xanthate quaternary ammonium salts are also excellent protectantsfor k-raft paper, but the chloride is relatively poor. The herbicidalactivity is quite superior to that of the chlorides.

Example VII Tetramethyl ammonium isopropyl xanthate was pre pared by theprocedures described above. This compound was crystalline and had lowerfungicidal, bactericidal and herbicidal activity when compared with thecoresponding xanthates in which one methyl group is replaced by aphenyl, a dodecyl, a lauryl pyridinium or a C18 group. It, nevertheless,can act as a mild germicide where plants need some protection fromcertain specific organisms. The melting point of this compound was 138-140 C.

Example VIII Cetyl dimethyl benzyl ammonium isopropyl xanthate wasprepared by dissolving the quaternary ammonium chloride in water andadding sodium isopropyl xanthate to Analysis 0 H charismaengin e g 269:95 10:36

'I'he 'xanthate derivative was much more effectivein killlng S. aureuswhen compared directly with the parent quaternary ammonium halide.

Example IX A solution, of 5 parts of p-diisobutylphenoxyethoxyethyldimethylbenz'yl ammonium chloride (also known by the trade name Hyamine1622) in excess isopropanol was .heated to 50 C., and. 2.5 parts ofsodium isopropyl xanthate were added. The mixture was held at 4050 C.for about an hour and it was then cooled to ice bath temperature. Thesodium chloride precipitated and was removed by filtration. The oilresidue from the alcohol solution was dissolved in benzene and washedthoroughly with wate'r. Thereafter the benzene was distilled to yield 6parts of an oil.v This was analyzed, and the following resultswereobtained:

Analysis a O H GalculatedforCa1HnNOaSz..- i 68:29 910s The originalquaternary ammonium chloride did not prevent the growth of algae at 10p. p. m. concentration in water, but the xanthate derivative completelyprevented growth under identical incubation conditions and at the sameconcentration. Also, the bactericidal activity of the xanthatequaternary against S. aureus was superior to the chloride. When testedby the filter paper disc method the clear zone with the xanthate was 2.9cm. and that of the chloride was 1.9 cm.

Example X 4.84 parts of n-dodecyl dimethyl methylcarboxyethyl ammoniumiodide in 10 parts of water were treated with 2.3 parts of sodiumisopropyl xanthate dihydrate at 40 to 50 C. The reaction mixture wasextracted with benzene and the benzene layer was dried with anhydroussodium sulfate. The benzene was then removed by vacuum distillation toyield 5 parts of a waxy solid with a melting point of to C. The xanthatederivative was superior to the iodide when compared directly forbactericidal activity against S. aureus in that a clear zone of 6centimeters was present in the test involving the iodide and a clearzone of 8 centimeters was present with the xanthate.

The remaining quaternary ammonium xanthates disclosed herein are alsomore eliective as bactericidal, fungicidal, insecticidal and herbicidalagents than are the parent quaternary ammonium chlorides, and any of thequaternary ammonium xanthates mentioned herein can be prepared byreacting the quaternary ammonium halide with an alkali metal lower alkylor alkylene xanthate.

Although I have described my invention by specific examples, they areintended to be illustrative only and not limiting, except as defined bythe appended claims, as it will be obvious to those skilled in the artthat various substitutions of ingredients and proportions can be madewithout departing from the spirit and scope of the 75 invention.

in which R and R1 each is a methyl group, R2 is selected from the classconsisting of methyl, phenyl and benzyl hydrocarbon groups. and R, R1and R2 collectively represent the hydrocarbon residue of a pyridinenucleus, and

R3 is selected from the class consisting of an aliphatic hydrocarbongroup having from 1 to 20 carbonatoms, a lower alkyl carboxyethyl group,a monocyclic aryl group, a monocyclic aryalkyl hydrocarbon group and ap-diisobutylphenoxyethoxyethyl group, and'Yis selected from the classconsisting of lower alkyl and alkenyl hydrocarbon groups having from 1to ,4 carbon atoms.

2. Trimethyl soya oil hydrocarbonammonium lower alkyl xanthate havingfrom 1 to 4 carbon atoms in the alkyl group. 1

3. Trimethyl coconut oil hydrocarbon ammonium lower alkyl xanthatehaving from 1 to 4 carbon atoms in the alkyl group.

4. Trimethyl phenyl ammonium lower alkyl xanthate having from 1 to 4carbon atoms in the alkyl group.

5. Dimethyl cetyl benzyl ammonium lower alkyl xanthate having from 1 to4 carbon atoms in the alkyl group.

6. Lauryl pyridinium lower alkyl xanthate having from 1 to 4 carbonatoms in the alkyl group.

7. Trimethyl soya oil hydrocarbon ammonium isopropyl xanthate.

8. Trimethyl coconut oil hydrocarbon ammonium isopropyl xanthate.

9. The method which comprises reacting a quaternary ammonium halide ofthe formula 1 7 in which R and R1 each is a methyl group, R2 is selectedfrom the class consisting of methyl, phenyl and benzyl hydrocarbon andcollectively said R,; R1 and R2 ,repre-I sent the hydrocarbon residue ofa pyridine nucleus, and: R: is selected from the class consisting ofaliphatic hydrocarbon groups having from 1 to 20 carbon atoms, a loweralkyl carboxy lower alkyl group, a monocyclic aryl group, a monocyclicaralkyl hydrocarbon group, and a p-diiso butylphenoxyethoxyethyl group,with ,a member selected from the class consisting of lower, alkyl andalkenyl alkali metal xanthates having from 1 tof4 carbon atomsinareaction medium selected from "the class consisting of water and aliquid'alkanol at a temperature up to about C. to thereby formaquaternaryamrnonium xan thate.

10. The method of claim, 9 in which the xanthate is isopropyl xanthateand the quaternary ammonium compound is a trimethyl soya oil hydrocarbonammonium halide.

11. The method of claim 9 in which the xanthate is isopropyl xanthateand the quaternary ammonium compound is a trimethyl coconut oilhydrocarbon ammonium halide.

12. The method of claim 9 in which the xanthate is isopropyl xanthateand the quaternary ammonium compound is a trimethyl n-dodecyl quaternaryammonium halide.

13. The method of claim 9 in which the xanthate is isopropyl xanthateand the quaternary ammonium compound is a dimethyl cetyl benzyl ammoniumhalide.

References Cited in the file of this patent UNITED STATES PATENTS

1. A COMPOUND HAVING THE GENERIC STRUCTURE